Condensates of imidazolidone derivatives and polyalkylene glycol useful for improving textile materials

ABSTRACT

NOVEL COMPOSITION OF MATTER IS PRODUCED BY REACTING 1 MOLE OF ALKYLATED DERIVATIVES OF 4,5-BIS-HYDROXY-1,3-BISHYDROXYMETHYL-IMIDAZOLIDONE-2 OF THE FORMULA,   1-(R&#39;&#39;-O-CH2-),2-(O=),3-(R4-O-CH2-),4-(R3-O-),5-(R2-O-)   IMIDAZOLIDINE   WHEREIN R1, R2, R3 AND R4 RESPECTIVELY REPRESENT HYDROGEN OR ALKYL HAVING 1 TO 4 CARBON ATOMS AND AT LEAST ONE MEMBER OF R1, R2, R3 AND R4 IS THE SAID ALKYL, WITH 0.2 TO 2 MOLES OF A WATER-SOLUBLE POLYALKYLENE GLYCOL HAVING A MOLECULAR WEIGHT OF 400 TO 10,000. THIS COMPOSITION OF MATTER IS USEFUL FOR IMPROVING HYDROPHOBIC SYNTHETIC TEXTILE MATERIALS OR BLENDS OF HYDROPHOBIC SYNTHETIC FIBERS AND CELLULOSIC FIBERS.

United States Patent 3,652,583 CONDENSATES OF IMIDAZOLIDONE DERIVA-TIVES AND POLYALKYLENE GLYCOL USE- FUL FOR IMPROVING TEXTILE MATERIALSShigeru Tajima, Ashiya-shi, Katsumi Kobayashi, Toyonaka-shi, HiroshiFukuhara, Osaka, Hiroki Yamamoto, Takarazuka-shi, and Shigeru Ura,Nishinomiya-shi, Japan, assignors to Sumitomo Chemical Company, Ltd.,Osaka, Japan No Drawing. Filed Mar. 11, 1969, Ser. No. 806,284 Claimspriority, application Japan, Mar. 14, 1968, 43/ 16,919 Int. Cl. C07d49/34 U.S. Cl. 260309.7 Claims ABSTRACT OF THE DISCLOSURE Novelcomposition of matter is produced by reacting 1 mole of alkylatedderivatives of 4,5-bis-hydroxy-1,3-bishydroxymethyl-imidazolidone-2 ofthe formula,

wherein R R R and R respectively represent hydrogen or alkyl having 1 to4 carbon atoms and at least one member of R R R and R is the said alkyl,with 0.2 to 2 moles of a water-soluble polyalkylene glycol having amolecular weight of 400 to 10,000.

This composition of matter is useful for improving hydrophobic synthetictextile materials or blends of hydrophobic synthetic fibers andcellulosic fibers.

The present invention relates to novel processes for the manufacture ofa composition of matter and the resulting composition of matter.Further, the present invention pertains to processes for improvngtextiles by impregnation with said composition and textiles resultingfrom said processes.

In general, polyester fibers and their blends are hydrophobic and havedisadvantages such as a lack of hydrophilic property, an easy soiling inwear or an insufficient soil-removal by washing.

It is important to overcome these disadvantages, and a number ofprocesses have been proposed in order to remove said drawbacks fromtextiles. For example, it has been known to give a soil-releasingproperty to synthetic textiles such as polyester textile by treatingthem with polyalkylene glycol such as polyethylene glycol. However, alow reactivity of the synthetic textile such as polyester textiles makesit difficult to improve the soil-releasing property with sufiicientdurability. On the other hand, there has heretofore been known a processfor improving hydrophobic synthetic textiles or mixed spun textiles ofhydrophobic synthetic fibers and cellulosic fibers by treating them witha composition of matter comprising urea, formaldehyde and glyoxal (forexample, US. Pat. No 3,049,446). However, the use of said composition ofmatter has given no satisfactory soil-releasing property.

The present inventors have found that a crease resistance and asoli-releasing property of hydrophobic synthetic textiles are broughtabout by treating the hydrophobic synthetic textiles with a compoundhaving both a group having an afiinity to the hydrophobic synthetictextiles and a group capable of reforming drawbacks of hydrophobicsynthetic textiles without imparing excellent intrinsic properties ofthe synthetic textiles. Further, the present inventors have found that acondensate obtained "Ice by an ester exchange reaction of alkylatedcompound of 4,5 bis-hydroxy-1,3-bis-hydroxymethyl-imidazolidone-Z and awater-soluble polyalkylene glycol is remarkedly suitable for thepurpose.

Accordingly, one object of the present invention is to provide a processfor preparing a composition of matter which is a condensate of awater-soluble polyalkylene glycol and alkylated compound of4,5-bis-hydroxyl-1,3-bishydroxymethyl-imidazolidone-Z.

Another object of the present invention is to provide a composition ofmatter obtained by the process described above.

A further object of the present invention is to provide a process forimproving properties of hydrophobic synthetic textiles or mixed spuntextiles of the hydrophobic synthetic fibers and cellulosic fibers withthe use of said composition of matter.

A still further object of the present invention is to provide improvedhydrophobic synthetic textiles or mixed spun textiles of hydrophobicsynthetic fibers and cellulosic fibers which have excellent creaseresisting and soilreleasing properties.

Other objects and further scope of applicability of the presentinvention will become apparent from the detailed description givenhereinbelow. It should be un-- derstood, however, that the detaileddescription and specific example-s are given by way of illustrationonly, Whose various changes and modifications within the spirit andscope of the invention will become apparent to those skilled in the artfrom this detailed description.

In order to accomplish these objects, the present invention provides aprocess for preparing a novel composition of matter, which comprisesreacting 1 mole of alkylated compound of4,5-bis-hydroxy-1,3-bis-hydroxymethyl-imidazolidone-2 represented by theformula,

0 II R1OCH2III N-CH1OR4 CH- H the 6R:

wherein R R 3 and R represent respectively hydrogen or alkyl having 1 to4 carbon atoms and at least one group of R R R and R is the said alkyl,with 0.2 to 2 moles of a water-soluble polyalkylene glycol having amolecular weight of 400 to 10,000.

Further, the present invention provides a composition of matter obtainedaccording to the above-mentioned process.

Further, the present invention provides a process for improvingproperties of hydrophobic synthetic textiles or mixed spun textiles ofhydrophobic synthetic fibers and cellulosie fibers, which comprisesimpregnating the textiles with an aqueous solution containing saidcomposition of matter and an acidic catalyst, squeezing the impregnatedtextiles, an amount of the composition of matter remained on thesqueezed textiles being 0.5 to 10% by weight of the textiles, drying thesqueezed textiles at a temperature of C. or below, and curing the driedtextiles at a temperature of to C.

The alkylated compound of4,5-bis-hydroxy-l,3-bishydroxymethyl-imidazolidone-Z is a knowncompound, and is produced by reacting, in the presence or absence of asolvent, urea, formaldehyde, glyoxal and a lower aliphatic alcoholhaving 1 to 4 carbon atoms. The lower alcohol is represented by thegeneral formula R OH, R OH, R OH or R OH, among which methanol ispreferable from the industrial and economical points of view. Only onekind or 2 to 4 kinds in combination of said 4 kinds of the alcohols maybe used. Examples of the solvent include water, same alcohol as used asthe reactant or a mixture thereof.

The foregoing reaction is carried out concretely by (l) Reacting urea,glyoxal, formaldehyde and a lower aliphatic alcohol having 1 to 4 carbonatoms in a single step, or

(2) Reacting 4,5-bis-hydroxy-imidazolidone-2 obtained by reacting ureawith glyoxal, with a lower aliphatic alcohol having 1 to 4 carbon atoms,and then reacting the resultant material with formaldehyde, or

(3) Reacting 4,S-bis-hydroxy-imidazolidone-2 obtained by reacting ureawith glyoxal, with formaldehyde, and then reacting the resultantmaterial with a lower aliphatic alcohol having 1 to 4 carbon atoms, or

(4) Reacting 4,5-bis-hydroxy-imidazolidone-2 obtained by reacting ureawith glyoxal, with formaldehyde and a lower aliphatic alcohol having 1to 4 carbon atoms in a single step, or

(5) Reacting N,N-bis-hydroxymetl1yl-urea or an initial condensatethereof obtained by reacting urea with formaldehyde, with glyoxal, andthen reacting the resultant material with a lower aliphatic alcoholhaving 1 to 4 carbon atoms, or

(6) Reacting N,N'-bis-hydroxymethyl-urea or an initial condensatethereof obtained by reacting urea with formaldehyde, with a loweraliphatic alcohol having 1 to 4 carbon atoms, and then reacting theresultant material with glyoxal, or

(7) Reacting an alkylated N,N-bis-hydroxymethylurea or an initialcondensate thereof obtained by reacting urea, formaldehyde and a loweraliphatic alcohol having 1 to 4 carbon atoms in a single step, withglyoxal, or

(8) Reacting urea, glyoxal and formaldehyde in a single step, and thenreacting the resultant material with a lower aliphatic alcohol having 1to 4 carbon atoms, or

(9) Reacting the resultant product obtained in accordance with any ofthe foregoing processes of (l) to (8), with a lower aliphatic alcoholhaving 1 to 4 carbon atoms.

Water-soluble polyalkylene glycols used in the present invention includepolyethylene glycol, polypropylene glycol, a copolymer consisting ofethylene glycol and propylene glycol.

The reaction or production of the present composition of matter iscarried out in the presence of an acid. Examples of the acid arep-toluene sulfonic acid, toluene- 2,4-disulfonic acid, sulfuric acid,nitric acid, hydrochloric acid and phosphoric acid. Employment of asolvent is not critical in the reaction, however, employment of water isadvantageous in the economical point of view. The reaction temperatureis within a range of 20 to 100 C.

The composition of matter thus produced is soluble in water, and theresultant aqueous solution can be used for the treatment of improvingthe textiles.

The textiles referred to in the present invention are hydrophobicsynthetic textiles, preferably polyester textiles, and mixed spuntextiles of hydrophobic synthetic fibers and cellulosic fibers.

In accordance with the present invention, the treatment of the textilesis carried out by impregnating the textile in an aqueous solution at thefirst time. Concentration of the composition of matter in the aqueoussolution is 0.1 to 20% (weight), preferably 1 to 10% (weight).

The acidic catalysts are used in the improvement of the presentinvention. The catalysts may be an organic acid, an inorganic acid or asalt of a strong acid and a weak base which is generally used for aresinous processing. Examples thereof include zinc nitrate, magnesiumchloride, diammonium hydrogen phosphate, ammonium chloride, mineral acidsalts of 2-amino-2-methyl propanol and ethanol amine, oxalic acid,maleic acid and the like, among which zinc nitrate or magnesium chlorideis preferable. Said catalyst is used in an amount of 1 to 100% byweight, preferably 5 to 50% by weight of the composition of matter.

The impregnation is carried out at a room temperature.

In an aqueous solution in the present process, an assistant usually usedmay be added. Examples of the assistants include methylol urea,dimethylol ethylene urea, dimethyloluron, dimethylol triazone,dimethylol glyoxal :rnono-urein, dimethylol propylene urea and analkylated compound thereof. The use of one kind or the combined use oftwo kinds of these assistants gives an effect further excellent indurability to textiles. The ratio of said assistant to the compositionof matter may be 20% by weight or more.

The impregnated textile is then squeezed to remove excess solution andprovide the desired amount of pick-up. In the present invention, a rateof the squeezing should be controlled in such a manner that an amount ofpickup to the textile of the composition of matter is 0.5 to 10% byweight of textile.

Subsequently, the impregnated textile is dried, followed by curing, orif required, the drying and curing can be performed at the same time.The drying is caried out at a temperature of C. or below and requiresabout 1 to 10 minutes. At the next time, the dried textiles are cured.The curing is carried out at a temperature of to C. and requires usuallyabout 30 sec. to 5 min. As the result, the composition of matter isconverted to an insoluble material.

The textiles improved by the present invention have an increasedhydrophilic property, a re-soil resistance and a soil releasing propertydue to a polyalkylene glycol chain. Further, the present composition ofmatter gives a large aflinity to hydrophobic synthetic fibers such aspolyester fibers and the like due to an imidazolidone ring, and has anexecellent durability due to reactivity with cellulosic fibers.Furthermore, in the case where there are many hydroxymethyl groups inthe composition of matter, an improved crease resistance of the treatedtextile can be obtained.

The following exampes are given merely as illustrative of the presentinvention and are not intended to limit the present invention.

EXAMPLE 1 4,5-bis (methoxy)-imidazolidone-2 obtained by methylating4,5-bis (hydroxy)-imidazolidone-2 was methylolated to1,3-bis-(hydroxymethyl) 4,5 bis-(methoxymethyl)-imidazolidone-2. To amixture of 62 g. of the resultant compound and g. of polyethylene glycolhaving a molecular weight of 600 was added 1.2 g. of para-toluenesulfonic acid, and heated at 60 C. for 40 minutes under a reducedpressure of about 50 mm. Hg. An amount of distilled methanol was 14.5 g.which corresponded to about 75% of the theoretical value. The resultantmaterial was immediately diluted with water and neutralized with a 5 Naqueous sodium hydroxide solution to obtain 450 g. of a 50% aqueoussolution.

The resultant solution was a light-yellowed transparent and viscoussolution.

EXAMPLE 2 Reaction of 2.5 moles of 37% formalin, 1.0 mole of 40%glyoxal, 1.0 mole of urea and 5 moles of isopropanol gave anisopropylated compound of1,3-bis-hydroxymethy1-4,5-bis-hydroxyimidazolidone-2 having 1.7 moles ofisopropoxy group. To a mixture of 57 g. of an isopropylated compound of1,3-bis-(hydroxymethyl)-4,5-bis-(hydroxy)- imidazolidone-2 and 300 g. ofmolten polyethylene glycol having a molecular weight of 2,000 Was added0.5 ml. of cone. hydrochloric acid and heated with stirring at 60 C. forone hour. To the resultant solution was added 50 ml. of water, then 1.2ml. of a 5 N aqueous sodium hydroxide solution was added thereto toneutralize the solution and thereafter 50 ml. of distillate were takenout under a reduced pressure. An amount of isopropanol in the distillatewas 10 g., which corresponded to 56% of the theoretical amount. Theresultant product was a compound wherein imidazolidone rings were bondedto both the terminals of polyethylene glycol.

EXAMPLE 3 Test items Re-soll resistance:

Reflection rate:

Dr 3 Degree of crease resistance (W-l-F) EXAMPLE 41,3-bis-(methoxymethyl) 4,5-bis-(hydroxy)-imidazolidone-2 used inExample 3 was reacted with an excessive amount of methanol to obtain amethylated compound of 1,3-bis-(hydaroxymethyl)-4,5 bis-(hydroxy)-imidazolidone-Z having a methylation degree of 3.5. 45.5 g. of theresultant methylated compound was reacted with 320 g. of a polyethyleneglycol-polypropylene glycol copolymer (50% of polyethylene glycol, 50%of polypropylene glycol) having a molecular weight of 800, in a mannersimilar to that of Example 3. An amount of the distilled methanol was 18g. which corresponded to 80% of the theoretical amount. The resultantproduct was a viscous solution capable of being optionally mixed withwater.

EXAMPLE Urea, 40% glyoxal and 37% formalin were mixed in a molar ratioof 1.0:1.0':2.5 respectively, and the resultant mixture was reacted atpH of 7.0 to 7.5 at 60 C. for 3 hours, and then the reaction product wasdehydrated and concentrated up to 90% of a solid. 10.0 moles of methanolwas added to the resultant solid, and the resultant mixture was reactedat a pH of 2.0 at C. for one hour, to obtain an initial condensate ofurea, glyoxal, formaldehyde and methanol having a methyla tion degree of1.5. 50 g. of an 80% aqueous solution of the resultant condensate wasmixed with 300 g. of polyethylene glycol having a molecular weight of1,500, and to the resultant mixture was added 0.5 ml. of 70% sulfuricacid and reacted at 7 0 C. for one hour. The re action rate was measuredfrom the produced methanol to be approximately 80%.

EXAMPLE 6 lMlXtlllC of 4,5-bis-(hydroxy)-imidazolidone-2, 37% formalinand methanol of a molar ratio of 1. 0:2.5 25.0 was heated at a pH of 5.2for 90 minutes under a reflux condition to obtain an initial condensateof CH O/N =0.55. A procedure similar to that of Example 5 was repeated,except that 41 g. of a 95% aqueous solution of the resultant condensatewas used in the place of the initial condensate of the Example 5 to givethe product at an ether interchange reaction rate of 73%.

Non-treated EXAMPLE 7 A 50% aqueous solution of each composition ofmatter obtained respectively in Examples 1, 2 and 3 was prepared. ATetoron-cotton (65/35) broadcloth was dipped into 100 ml. of a bathcontaining water and 15 g. of said 50% aqueous solution of resin and 4.5g. of 30% aqueous solution of magnesium chloride, squeezed by a mangleso as to maintain an amount of pick-up of the composition of matter at7.0% per an amount of the cloth, then dried at C. for 2 minutes, andthereafter cured at 160 C. for 3 minutes. Subsequently, after effectinghome laundering of one to three times, a re-soil resistance property ofthe treated cloth was tested. Further, a degree of crease resistance ofthe resultant cloth was measured. As shown in Table 1, the resultsindicate conspicuously favourable durability and re-soil resistance andbring about an improvement in the degree of crease resistance.

TABLE 1 Treated cloth Cloth treated by composition in Example 3 Clothtreated by ST precl h scription Remarks:

(1) The ST prescription referred to herein means a case where1,3-bis-(hydroxymethyl) 4,5 bis-(hyd1'oxy)- imidazolidone-Z is used inplace of the composition of matter of the present invention.

(2) A method for testing a re-soil resistancen (a) Artificial oily soil:A mixture consisting of 12.5% (all percent: by weight) of stearic acid,12.5% of oleic acid, 12.5% of coconut hardened oil, 12.5% of olive oil,8.5% of cetyl alcohol, 21.5% of solid parafiin, 5.0% of cholesterol and'15.0% of carbon black.

(b) Artificial solid soil: A mixture consisting of 55% of clay, 17% ofsilicic anhydride, 0.5% of ferric oxide, 17% of portland cement, 8.75%of n-heptame and 1.75% of carbon black.

3 parts of a mixture composed of the artificial oily soil (3) Degree ofsoil redeposition o-Rs 1(01' Rs 3) D8 1 (or D8 3 R0 x R0: A reflectionrate of the treated cloth prior to soiling.

Rs: A reflection rate of the treated cloth after soiling.

Rs 1 and Rs 3: Reflection rates of the treated cloths which weresubjected to home launderings of '1 and 3 times respectively and thentreated with soiling.

Test Method of Crease Resistance:

Monsanto Method (JIS 'L-1041 C Method) (W-l-F): (Warp-i-Filling recoveryangle) (degree) 7 EXAMPLE 8 A bath (100 ml.) was prepared from 8 g. ofthe composition of matter obtained in (Example 2, .15 g. of a 50%aqueous solution of 4,5bis-(hydroxy)1,3-(hydroxymethyl)-imidazolidone-2and 4.5 g. of a 30% aqueous solution of magnesium chloride with anaddition of water. A Tetoron-cotton (65/35) broadcloth was dipped intothe resultant bath, squeezed by a mangle to maintain an amount ofpick-up of the composition of matter at 7.0% per an amount of the cloth,dried at 80 C. for 2 minutes and then cured at 160 C. for 3 minutes. Are-soil resistance and a rigidity of the cloth thus treated weremeasured, the result of which is shown in Table 2.

TABLE 2 Treated cloth Non- Cloth treated Cloth treated in treated by STpreaccordance with Test items cloth scription this example Degree ofsoil redeposition,

percei Dsl 25.0 26.0 6. D s 3 23. 5 25. 0 6. b Rigidity (g./20 mm.) 89100 93 Remarks:

(1) The cloth treated by ST prescription referred to herein means onewhich is treated with 4,5-bis-(hydroxy) -1,3-bis- (hydroxymethyl-imidazolidone-2 alone according to the treatment of the presentexample.

(2) The rigidity was measured by means of a handle-ometer made by ThwingAlbert Instrument Co.

From the foregoing Table 2, it is found that a re-soil resistance with asuperior durability is obtained by the combined use of a prior knownprocessing agent with the composition of matter obtained in Example 2without being influenced badly on a feeling in touch.

The composition of matter obtained in Example 5 also showed favourableperformances in the similar degree to that obtained in Example 2.

EXAMPLE 9 The composition of matter obtained in Example 3 was used incombination with a prescribed agent for a permanent press processing. Aprocessing with the use of said combination was carried out just in thesame manner as in Example 8. The result is shown in Table 3.

Remark:

(1) The motor-oil releasing property referred to herein means a soilreleasing property when a drop of motoroil (made by Maruzen Sekiyu K.K.,No. 40) is attached on a cloth and the resultant cloth is subjected toone time of home laundering. A degree of releasing property was judgedon the following standard:

1: not entirely released. 2: somewhat released. 3: released ordinarily.4: almost completely released. 5: completely released.

From the foregoing table, it is found that the combined use of thepresent composition of matter with the prescribed agent for thepermanent press processing shows a favourable re-soil resistance and amotor-oil releasing property without influencing badly on a W & Wproperty (wash and Wear property) and a feeling in touch (rigidity) ofpermanent press-processed cloth.

What we claim is 1. A process for preparing a novel composition ofmatter, which comprises reacting 1 mole of an alkylated compound of4,5-bis-hydroxy-1,3-bis-hydroxymethylimidazolidone-2 represented by theformula,

0 C R1OCHZN/ \NCH2OR4 (JH('JE 0R 0R wherein R R R and R respectivelyrepresent hydrogen or alkyl having 1 to 4 carbon atoms, at least onegroup of R R R and R being the said alkyl, with 0.2 to 2 moles of awater-soluble polyalkylene glycol having a molecular weight of 400 to10,000, wherein the reaction is carried out in the presence of an acidat a temperature of 20 C. to C.

2. A process according to claim 1, wherein the alkyl of R R R or R ismethyl.

3. A process according to claim 1, wherein the Watersoluble polyalkyleneglycol is polyethylene glycol, polypropylene glycol or a copolymerconsisting of ethylene glycol and propylene glycol.

4. A process according to claim 1, wherein the acid is p-toluenesulfonic acid, toluene-2,4-disulfonic acid, hydrochloric acid, sulfuricacid, nitric acid or phosphoric acid.

5. A composition of matter produced according to a process as claimed inclaim 1.

References Cited UNITED STATES PATENTS 3,029,164 4/1962 Seki et a1260309.7 3,427,121 2/1969 Frick et a1. 81l5.6

OTHER REFERENCES Harper et al. Textile Research Journal, vol. 38, No.(3) pp. 292-304, March 1968.

HENRY R. JILES, Primary Examiner R. T. BOND, Assistant Examiner US. Cl.X.R. 117-4395, 138.8

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,652,583 r Dated April '28, 1972 Inventor(s') Shigeru Taj ima et a1.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

In column liafter line 12, please insert the following missing claim forpriority:

-Ja'panese ApplnrNor' 28l88-filedApril 26, 1968-- Signed and sealed this17th day of October 1972.

(SEAL) Attest:

.EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents "ORM PO-OSO (10-69) USCOMM-DC 60376-P69 h as GOVERNMENTrmm'ms OFFICE: I969 o ns-:3!

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3652,583 Dated April 1972 Inventor(s) Shigeru Taj ima et a1.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

In column 1, I after line 12, please insert the following missing claimfor priority:

-Japanese Appln. No. 28188- filed April 26, 1968-- Signed and sealedthis 17th day of October 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents 'ORM PO-IOSO (10-69) USCOMM-DC 603764- 09 w us. GOVERNMENTrmm'mc OFFICE: I969 0-J66-.\J4

